CN104466166A - Preparation method of nickel-manganese spinel high-voltage positive material of lithium secondary battery - Google Patents

Preparation method of nickel-manganese spinel high-voltage positive material of lithium secondary battery Download PDF

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CN104466166A
CN104466166A CN201410764223.5A CN201410764223A CN104466166A CN 104466166 A CN104466166 A CN 104466166A CN 201410764223 A CN201410764223 A CN 201410764223A CN 104466166 A CN104466166 A CN 104466166A
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nickel
solution
preparation
manganese
positive electrode
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冯季军
王雪华
郭琳昱
李水华
刘永
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University of Jinan
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses an organic coprecipitation preparation method of a nickel-manganese spinel high-voltage positive material LiNi0.5Mn1.5O4 of a lithium secondary battery. The organic coprecipitation preparation method is characterized by comprising the following steps: weighing a lithium source, a nickel source and a manganese source according to a stoichiometric ratio, dissolving the sources into deionized water to obtain a solution A, dissolving an organic precipitating agent to obtain a solution B, and mixing the solution A and the solution B to generate a precipitation; and then directly evaporating to remove a solvent without carrying out filtering and precipitation washing to obtain a precursor, and then carrying out heat treatment to obtain the target product LiNi0.5Mn1.5O4. According to the organic coprecipitation preparation method, Ni<2+> and Mn<2+> ions are compounded with the organic precipitating agent through coordination bonds in the forming process of the precipitation, so that the very high ionic selectivity is achieved; in addition, the precipitating agent can be removed by being decomposed in a sintering process, so that the precipitation is unnecessary to wash, not only is a preparation process simplified, but also the stoichiometric ratio of a product can be well controlled, and the process control and the product purity and property have the very good repeatability.

Description

A kind of preparation method of lithium secondary battery nickel galaxite high-voltage anode material
Technical field
The present invention relates to a kind of lithium secondary battery high-voltage anode material nickel galaxite LiNi 0.5mn 1.5o 4preparation method, especially relate to the method utilizing Cobalt legal system for highly purified nickel galaxite positive electrode material of lithium secondary cell, belong to lithium secondary battery field of material technology.
Background technology
Voltage is high owing to having for lithium secondary battery, energy density is large, have extended cycle life, memory-less effect, self discharge are little and the good characteristic such as environmental friendliness and become one of best battery system of current combination property, be widely used in the various fields such as photoelectricity, information, traffic, national defense and military and Aero-Space, and become the leading role of energy-storage battery and automobile power cell.Lithium secondary battery wants to obtain faster and better development in this new energy development upsurge, and the improvement of material is basic.High power, high-energy-density, the research of high security, long-life, environmental friendliness, low cost electrode material is the emphasis of lithium secondary battery industry development always.
For making electrokinetic cell obtain higher power and energy density, research and development high-voltage anode material becomes the task of top priority [8].Along with the progress of electrolyte and additive thereof, improve the resistance to oxidation current potential of electrolyte, make the practical of high-voltage anode material become possibility.Therefore, there is the spinelle LiMe of 5V level intercalation potential x mn 2- x o 4series material highly causes concern.Wherein, LiNi 0.5mn 1.5o 4theoretical energy density can reach 690Whkg -1, be a kind of power positive electrode material of lithium secondary cell having prospect.
At LiNi 0.5mn 1.5o 4in, manganese is+4 valencys and remains unchanged in embedding/de-lithium process, and the capacity at 4.7V place comes from Ni 2+/3+/4+oxidation/reduction reaction.Because the periodic regularity of nickel manganese arrangement is different, spinelle LiNi 0.5mn 1.5o 4there are two kinds of different crystal structures.Ni-Mn arranges orderly LiNi 0.5mn 1.5o 4, Ni 2+and Mn 4+occupy-place can distinguish, in simple cubic spinel structure, belong to p4 332 space groups.Ni-Mn arranges unordered LiNi 0.5mn 1.5o 4-in face-centered cubic spinel structure, Ni 2+, Mn 4+with a small amount of Mn brought due to oxygen defect 3+be randomly dispersed in the position of octahedra 16d, be similar to pure spinelle LiMn 2o 4, belong to fd3 mspace group.
LiNi 0.5mn 1.5o 4structure and preparation method closely related, to synthesis temperature and atmosphere very responsive.Solid phase method is the classical preparation method of nearly all positive electrode, but it is high to there is energy consumption, and batch wise differences is large, the shortcomings such as domain size distribution is wide.To spinelle LiNi 0.5mn 1.5o 4, on the one hand, easily form oxygen disappearance in sintering process, and cause NiO and Li x ni 1- x existence (the 5V positive electrode LiNi of the dephasigns such as O 0.5mn 1.5o 4self-propagating Sintering Synthetic and performance, Chinese Journal of Inorganic Chemistry, 2009,25:124-128.), destroy the cyclical stability of material; On the other hand, concerning the embedding oxidate for lithium of this type of hybrid transition metal based on solid solution, how accurately controlling the stoichiometric proportion of product, is also the problem needing to solve in material preparation process.Therefore, suitable preparation method is most important to electrode material.Not only can obtain by selecting suitable preparation method that particle size shape is suitable for, the controllable appearance of even particle size distribution, more can obtain better crystallinity, higher phase purity and structural stability, thus realize more excellent chemical property.
The synthetic method of a series of nano material, is just progressively incorporated in the preparation of electrode material studied person.Yang Yong adopts water heat transfer spinelle LiNi 0.5mn 1.5o 4, material particle size, at about 30nm, presents good high rate performance (Hydrothermal Synthesis of a Nanosized LiNi 0.5mn 1.5o 4cathode Material for High Power Lithium-Ion Batteries, J. Electrochem. Soc., 2011,158:A139-A145.).Cui is with-MnO 2for precursor, prepare the manganese system spinel superfine nanowire that diameter is less than 10nm, demonstrate superior high rate performance (Ultrathin Spinel LiMn 2o 4nanowires as High Power Cathode Materials for Li-Ion Batteries, Nano Lett., 2010,10:3852-3856.).Wang Jianming take NaOH as precipitation reagent, adopts coprecipitation to prepare LiNi 0.5mn 1.5o 4, material circulation performance is improved (Physical Properties and Electrochemical Performance of LiNi 0.5mn 1.5o 4cathode Material Prepared by a Coprecipitation Method, Mater. Chem. Phys., 2007,103:19-23.).Coprecipitation is approved because it can control the element proportioning in precursor preferably, but the coprecipitation of research is at present all using inorganic base as precipitation reagent, and is avoid precipitation reagent to remain the destruction of OH to material property, needs repeatedly to wash precipitation.No matter and the solution loss in washing process, in washing process, to change the loss of elements brought unbalanced for pH value, still can bring difficulty to the Composition Control of material.In addition, even if pass into inert gas in precipitation process in system, be also difficult to avoid a small amount of ion to be oxidized to high-valence state, this, also for calculating that Li source addition brings uncertainty according to precursor gravimetric method, causes product stoichiometry ratio to be difficult to control.For this reason, the present invention introduces organic precipitant in a creative way, can solve the problem well, and can simplify preparation technology.Utilize organic precipitant coprecipitation, the positive electrode that can be based on solid solution synthesizes, and brings following advantage: (1) organic precipitant is combined with coordinate bond with metal ion, has good ion selectivity, and the precipitation of generation is pure and solubility is very little; (2) select suitable precipitation reagent, precipitation nucleation can be made to separate with growth course, thus control nucleus is synchronously grown up, and obtains the molecule of size uniform; (3) organic precipitant can decompose removing in sintering process, therefore can washing precipitation precursor, thus both simplifies preparation technology, can control again the stoichiometric proportion of product well.
Summary of the invention
The object of the invention is to for LiNi 0.5mn 1.5o 4be difficult to the stoichiometric proportion accurately controlling product in preparation process, form Li x ni 1- x o dephasign and cause the problems such as chemical property variation, provide a kind of technological operation simple, product purity is high, and the Cobalt preparation method of the nickel galaxite high-voltage anode material of electrochemical performance.
Preparation method of the present invention comprises the following steps:
1) the solubility Li source compound of certain stoichiometric proportion, nickel source compound and manganese source compound are added to the water respectively, dissolve, be uniformly mixed after obtain mixed solution A;
2) weigh organic precipitant according to the certain proportion with metal ion, be dissolved under uniform temperature in organic solvent, obtain solution B;
3) under continuous stirring, by the mixed solution A of step 1) gained and step 2) solution B of gained mixes in the mode dropwise dripped, is added dropwise to complete rear continuation and stirs a period of time, constantly generate precipitation in this process;
4) by the precipitated dispersion system of step 3) gained, without the need to filtering and washing of precipitate, direct evaporation drying is removed desolventizing and is precipitated thing;
5) sediment of step 4) gained is obtained presoma after pre-burning;
6) under certain atmosphere, rise to high temperature sintering a period of time with certain heating rate by after the presoma of step 5) gained under a certain pressure base, after being then cooled to room temperature with certain rate of temperature fall, grind and obtain target product nickel galaxite LiNi 0.5mn 1.5o 4.
The mol ratio of described Li source compound, nickel source compound and manganese source compound is 2:1:3, and wherein lithium source can be suitably excessive.
Described Li source compound is at least one in lithium acetate, lithium oxalate, lithium fluoride, lithium hydroxide, lithium carbonate.
Described nickel source compound is at least one in nickel acetate, nickel oxalate, nickel nitrate, nickel chloride.
At least one in described manganese source compound manganese acetate, manganese oxalate, manganese nitrate, manganese chloride.
The ratio of described organic precipitant and metal ion " n(precipitation reagent): n(total metal ion) " be (1 ~ 3): 1.
Described organic precipitant is at least one in dimethylglyoxime, oxine, sodium tetraphenylborate, crystal violet, peacock green, methylene blue, dinitroaniline etc.
Described organic solvent is at least one in methyl alcohol, ethanol, isopropyl alcohol, cyclohexane, acetonitrile, 1-METHYLPYRROLIDONE, DMF etc.
The described hybrid mode dropwise dripped is for be dropwise added drop-wise to solution A in solution B, or solution B is dropwise added drop-wise in solution A, or solution A and solution B is dropwise added drop-wise in another container simultaneously.
Described precipitated dispersion system evaporation drying except the mode of desolventizing be heating water bath evaporation, drying box dries, at least one in vacuumize, baking temperature is 60 ~ 120 DEG C.
The pressure of described precursor powder compressing tablet base is 1 ~ 10MPa.
Described sintering atmosphere is at least one in air, oxygen, nitrogen, argon gas, helium.
Described calcined temperature is 200 ~ 650 DEG C, and burn-in time is 1 ~ 8h; Calcination process heating rate is intensification per minute 1 ~ 20 DEG C, and calcining heat is 600 ~ 900 DEG C, and calcination time is 2 ~ 24h.
The described type of cooling is program control slow cooling, in stove, cooling, post-calcination sample directly take out fast cooling, sample is dropped into quenching-in water naturally, sample is dropped at least one in quenching in liquid nitrogen.
Accompanying drawing explanation
In order to be illustrated more clearly in technical scheme of the present invention, in describing the present invention and embodiment below, the required accompanying drawing used does simple introduction.Apparently, the accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, can also obtain other accompanying drawings according to these accompanying drawings.
Fig. 1 is LiNi prepared by the present invention 0.5mn 1.5o 4the x-ray diffraction pattern of positive electrode sample.For ease of comparing, give the x-ray diffraction pattern that solid phase method prepares nickel galaxite positive electrode in Fig. 1, be belong to Li in black circle in figure simultaneously x ni 1- x the diffraction maximum of O dephasign.As seen from Figure 1, the LiNi prepared by Cobalt preparation method of the present invention 0.5mn 1.5o 4material crystalline is good, and phase purity is high, and dephasign diffraction peak intensity obviously reduces, and is even close to disappearance.This absolutely proves, Cobalt method can suppress the generation of rock salt dephasign and oxygen defect well.
Fig. 2 is LiNi prepared by the present invention 0.5mn 1.5o 4the scanning electron microscope (SEM) photograph of positive electrode sample.As seen from Figure 2, prepared LiNi 0.5mn 1.5o 4material granule good dispersion, presents smooth surface, and shape is regular, the octahedra shape of class of size uniform.Octahedra shape is the result of crystal along (111) crystal face dominant growth, makes it have better thermal stability.
Fig. 3 is LiNi prepared by the present invention 0.5mn 1.5o 4the discharge curve of positive electrode sample under different multiplying electric current.As seen from Figure 3, prepared LiNi 0.5mn 1.5o 4material still has good high rate performance when not extra carbon dope.
Fig. 4 is LiNi prepared by the present invention 0.5mn 1.5o 4the charge and discharge cycles curve chart of positive electrode sample.As seen from Figure 4, prepared LiNi 0.5mn 1.5o 4material has good cycle performance and reaction invertibity.
Embodiment
For the ease of understanding the present invention, below in conjunction with specific embodiment, the present invention is described in further detail.Obviously, described embodiment is only section Example of the present invention, instead of whole embodiments.Based on embodiments of the invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to protection scope of the present invention.
Embodiment 1
0.02mol lithium acetate, 0.01mol nickel acetate, 0.03mol manganese acetate are added in deionized water respectively, dissolve, be uniformly mixed after obtain mixed solution A; Take 0.08mol organic precipitant oxine, be dissolved at 60 DEG C in ethanol, obtain solution B.Under continuing magnetic force stirs, slowly solution A is dropwise added drop-wise in solution B, is added dropwise to complete rear continuation and stirs 2h, in this process, constantly generate precipitation.This precipitated dispersion is tied up to 80 DEG C of water-bath evaporation of solvent, then in 110 DEG C of air dry ovens dry 10h, be precipitated thing.The sediment of gained is obtained presoma after 300 DEG C of pre-burning 2h.At 10MPa tableting under pressure base after presoma is ground, rise to 800 DEG C of insulation 10 h with the heating rate of 10 DEG C/min in air atmosphere, after being then cooled to room temperature with the rate of temperature fall of 1 DEG C/min, grind and obtain target product nickel galaxite LiNi 0.5mn 1.5o 4.The X-ray powder diffraction figure of sample, see Fig. 1, shows that products therefrom is LiNi 0.5mn 1.5o 4.By comparing visible with sample prepared by solid phase method, the LiNi prepared by the present invention 0.5mn 1.5o 4material crystalline is good, and phase purity is high, does not almost have dephasign.The scanning electron microscope (SEM) photograph of sample is see Fig. 2, and the even particle size of product as seen from the figure, particle diameter is about 150nm.Using the product of gained as positive electrode, experiment button lithium secondary battery is assembled in the glove box being full of argon gas, in the potential region of 3.3 ~ 4.9V, charge and discharge cycles is carried out with the multiplying power of 0.2C, specific discharge capacity can reach 130 more than mAh/g, specific discharge capacity under 10C multiplying power can reach 75 more than mAh/g, reversible capacity after circulating 90 weeks still can remain on more than 105mAh/g, demonstrates excellent chemical property.
Embodiment 2
0.03mol lithium oxalate, 0.015mol nickel oxalate, 0.045mol manganese oxalate are added in deionized water respectively, dissolve, be uniformly mixed after obtain mixed solution A; Take 0.10mol organic precipitant dinitroaniline, be dissolved at 50 DEG C in cyclohexane, obtain solution B.Under continuing magnetic force stirs, slowly solution B is dropwise added drop-wise in solution A, is added dropwise to complete rear continuation and stirs 3h, in this process, constantly generate precipitation.This precipitated dispersion is tied up to 80 DEG C of water-bath evaporation of solvent, then in 120 DEG C of dried in vacuo overnight, be precipitated thing.The sediment of gained is obtained presoma after 400 DEG C of pre-burning 5h.At 8MPa tableting under pressure base after presoma is ground, under oxygen atmosphere, rise to 750 DEG C of insulation 20 h with the heating rate of 5 DEG C/min, after being then cooled to room temperature with the rate of temperature fall of 0.5 DEG C/min, grind and obtain target product nickel galaxite LiNi 0.5mn 1.5o 4.
Embodiment 3
0.02mol lithium hydroxide, 0.01mol nickel chloride, 0.03mol manganese chloride are added in deionized water respectively, dissolve, be uniformly mixed after obtain mixed solution A; Take 0.06mol organic precipitant dimethylglyoxime, be dissolved at 40 DEG C in isopropyl alcohol, obtain solution B.Under continuing magnetic force stirs, slowly solution A and solution B are dropwise added drop-wise in beaker simultaneously, in this process, constantly generate precipitation, be added dropwise to complete rear continuation and stir 5h.This precipitated dispersion is tied up to 70 DEG C of water-bath evaporation of solvent, then in 120 DEG C of air dry ovens dry 12h, be precipitated thing.The sediment of gained is obtained presoma after 470 DEG C of pre-burning 3h.At 12MPa tableting under pressure base after presoma is ground, rise to 850 DEG C of insulation 6 h with the heating rate of 15 DEG C/min in a nitrogen atmosphere, after then cooling to room temperature with the furnace, grind and obtain target product nickel galaxite LiNi 0.5mn 1.5o 4.
Embodiment 4
0.01mol lithium carbonate, 0.005mol nickel nitrate, 0.015mol manganese nitrate are added in deionized water respectively, dissolve, be uniformly mixed after obtain mixed solution A; Take 0.45mol organic precipitant dinitroaniline, be dissolved at 60 DEG C in 1-METHYLPYRROLIDONE, obtain solution B.Under continuing magnetic force stirs, slowly solution A is dropwise added drop-wise in solution B, in this process, constantly generates precipitation, be added dropwise to complete rear continuation and stir 6h.This precipitated dispersion is tied up to 80 DEG C of water-bath evaporation of solvent, then in 120 DEG C of vacuumize 16h, be precipitated thing.The sediment of gained is obtained presoma after 600 DEG C of pre-burning 2h.At 6MPa tableting under pressure base after presoma is ground, 800 DEG C of insulation 12 h are risen in air atmosphere with the heating rate of 8 DEG C/min, then sample is directly taken out to drop in deionized water at room temperature and quench, dried overnight in 120 DEG C of air dry ovens again, namely obtains target product nickel galaxite LiNi after grinding 0.5mn 1.5o 4.

Claims (9)

1. a lithium secondary battery nickel galaxite high-voltage anode material LiNi 0.5mn 1.5o 4cobalt preparation method, it is characterized in that adopting organic precipitant coprecipitation to prepare this material, organic precipitant can decompose removing in sintering process, therefore can washing precipitation precursor, thus both simplify preparation technology, the stoichiometric proportion of product can be controlled again well, mainly comprise the following steps:
1) the solubility Li source compound of certain stoichiometric proportion, nickel source compound and manganese source compound are added to the water respectively, dissolve, be uniformly mixed after obtain mixed solution A;
2) weigh organic precipitant according to the certain proportion with metal ion, be dissolved under uniform temperature in organic solvent, obtain solution B;
3) under continuous stirring, by the mixed solution A of step 1) gained and step 2) solution B of gained mixes in the mode dropwise dripped, is added dropwise to complete rear continuation and stirs a period of time, constantly generate precipitation in this process;
4) by the precipitated dispersion system of step 3) gained, without the need to filtering and washing of precipitate, direct evaporation drying is removed desolventizing and is precipitated thing;
5) sediment of step 4) gained is obtained presoma after pre-burning;
6) under certain atmosphere, rise to high temperature sintering a period of time with certain heating rate by after the presoma of step 5) gained under a certain pressure base, after being then cooled to room temperature with certain rate of temperature fall, grind and obtain target product nickel galaxite LiNi 0.5mn 1.5o 4.
2. the Cobalt preparation method of nickel galaxite positive electrode as claimed in claim 1, is characterized in that the mol ratio of described Li source compound, nickel source compound and manganese source compound is 2:1:3; Described Li source compound is at least one in lithium acetate, lithium oxalate, lithium fluoride, lithium hydroxide, lithium carbonate, described nickel source compound is at least one in nickel acetate, nickel oxalate, nickel nitrate, nickel chloride, at least one in described manganese source compound manganese acetate, manganese oxalate, manganese nitrate, manganese chloride.
3. the Cobalt preparation method of nickel galaxite positive electrode as claimed in claim 1, it is characterized in that described organic precipitant and metal ion ratio " n(precipitation reagent): n(total metal ion) " be (1 ~ 3): 1; Described organic precipitant is at least one in dimethylglyoxime, oxine, sodium tetraphenylborate, crystal violet, peacock green, methylene blue, dinitroaniline etc.; Described organic solvent is at least one in methyl alcohol, ethanol, isopropyl alcohol, cyclohexane, acetonitrile, 1-METHYLPYRROLIDONE, DMF etc.
4. the Cobalt preparation method of nickel galaxite positive electrode as claimed in claim 1, the hybrid mode dropwise dripped described in it is characterized in that is for be dropwise added drop-wise to solution A in solution B, or solution B is dropwise added drop-wise in solution A, or solution A and solution B are dropwise added drop-wise in another container simultaneously.
5. the Cobalt preparation method of nickel galaxite positive electrode as claimed in claim 1, it is characterized in that described precipitated dispersion system evaporation drying except the mode of desolventizing be heating water bath evaporation, drying box dries, at least one in vacuumize, baking temperature is 60 ~ 120 DEG C.
6. the Cobalt preparation method of nickel galaxite positive electrode as claimed in claim 1, is characterized in that the pressure of described precursor powder compressing tablet base is 1 ~ 10MPa.
7. the Cobalt preparation method of nickel galaxite positive electrode as claimed in claim 1, is characterized in that described sintering atmosphere is at least one in air, oxygen, nitrogen, argon gas, helium.
8. the Cobalt preparation method of nickel galaxite positive electrode as claimed in claim 1, it is characterized in that described calcined temperature is 200 ~ 650 DEG C, burn-in time is 1 ~ 8h; Calcination process heating rate is intensification per minute 1 ~ 20 DEG C, and calcining heat is 600 ~ 900 DEG C, and calcination time is 2 ~ 24h.
9. the Cobalt preparation method of nickel galaxite positive electrode as claimed in claim 1, it is characterized in that the described type of cooling is program control slow cooling, cooling, post-calcination sample directly take out fast cooling, sample is dropped into quenching-in water naturally in stove, sample is dropped at least one in quenching in liquid nitrogen.
CN201410764223.5A 2014-12-15 2014-12-15 Preparation method of nickel-manganese spinel high-voltage positive material of lithium secondary battery Pending CN104466166A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105070902A (en) * 2015-07-17 2015-11-18 济南大学 Mixed transition metal based preparation method for cathode material of sodium secondary battery
CN105185976A (en) * 2015-08-14 2015-12-23 东莞市迈科科技有限公司 Lithium-ion battery cathode material nickel-cobalt lithium aluminate and preparation method thereof
CN107069023A (en) * 2017-03-30 2017-08-18 合肥工业大学 A kind of preparation method of hollow-core construction lithium ion battery electrode material
CN112978809A (en) * 2019-12-18 2021-06-18 格林美股份有限公司 Core-shell structure aluminum-doped nickel-cobalt-manganese cathode material precursor and preparation method thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105070902A (en) * 2015-07-17 2015-11-18 济南大学 Mixed transition metal based preparation method for cathode material of sodium secondary battery
CN105185976A (en) * 2015-08-14 2015-12-23 东莞市迈科科技有限公司 Lithium-ion battery cathode material nickel-cobalt lithium aluminate and preparation method thereof
CN107069023A (en) * 2017-03-30 2017-08-18 合肥工业大学 A kind of preparation method of hollow-core construction lithium ion battery electrode material
CN112978809A (en) * 2019-12-18 2021-06-18 格林美股份有限公司 Core-shell structure aluminum-doped nickel-cobalt-manganese cathode material precursor and preparation method thereof
CN112978809B (en) * 2019-12-18 2023-05-09 格林美股份有限公司 Core-shell structure aluminum-doped nickel-cobalt-manganese positive electrode material precursor and preparation method thereof

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